CN113980435A

CN113980435A - PBT resin with low dyne value and preparation method thereof

Info

Publication number: CN113980435A
Application number: CN202111563070.4A
Authority: CN
Inventors: 王尹杰; 申维新; 石景丽; 岳同健
Original assignee: Shanghai Sunny Technology Co ltd
Current assignee: Shanghai Sunny Technology Co ltd
Priority date: 2021-12-20
Filing date: 2021-12-20
Publication date: 2022-01-28
Anticipated expiration: 2041-12-20
Also published as: CN113980435B

Abstract

The invention provides a PBT resin with a low dyne value and a preparation method thereof, wherein the PBT resin with the low dyne value comprises the following components in parts by weight: 100 parts of polybutylene terephthalate (PBT); 8-20 parts of polypropylene GMA graft; 0.5-2 parts of crystallization inhibitor; 0.01-0.05 part of catalyst. The preparation method of the PBT resin with the low dyne value comprises the following steps: s1, weighing the following components in parts by weight: 100 parts of polybutylene terephthalate, 8-20 parts of polypropylene GMA graft, 0.5-2 parts of crystallization inhibitor and 0.01-0.05 part of catalyst. And S2, fully and uniformly mixing the components in the step S1 by a high-speed mixer, extruding by a double-screw extruder, and granulating to obtain the PBT resin with a low dyne value. The low-dyne-value PBT resin has a dyne value lower than 38, has no precipitation risk, and can be applied to the fields of PCB packaging and the like which need low-dyne-value application.

Description

PBT resin with low dyne value and preparation method thereof

Technical Field

The invention relates to the technical field of high polymer materials, in particular to a PBT resin with a low dyne value and a preparation method thereof.

Background

A Printed Circuit Board (PCB) is formed on a general-purpose substrate in a predetermined design. In the PCB manufacturing process, a release film is usually used for protection and isolation in the lamination (e.g. cover film, PI film, pure plastic steel sheet, etc.). At present, silicone oil transfer in different degrees can be generated after high-temperature pressing of common organic silicon release films in the prior art, which is shown in that residual silicone oil or mist substances exist on the surfaces of the films, and further the peeling strength of the bonding surfaces of the subsequent processes is reduced and even does not reach the standard. While the non-silicon release materials are mainly TPX, PTFE, FEP and the like, the release materials with low dyne values are too high in price and not suitable for being applied to pressing operation in large batch.

Polybutylene terephthalate (PBT) is one of five engineering plastics, and is a semi-crystalline engineering plastic. Has good mechanical property, electrical property, chemical resistance and the like, and is widely applied to the fields of electronic appliances, automobiles and the like. However, because the surface tension of PBT is very high, it is difficult to separate PBT from the target, and thus the application of PBT in the fields of films, especially PCB packaging, etc. is limited. There are few reports on low dyne PBT resins, as in CN105440604A by adding external lubricating type aids such as: oxidized polyethylene wax, stearate, stearic acid amide, etc. to lower the dyne value of the surface of PBT, but the effect of lowering is limited and there is a risk of precipitation when added in large amounts.

Disclosure of Invention

Aiming at the defects in the prior art, the invention aims to provide a PBT resin with a low dyne value and a preparation method thereof. Can be applied to various fields of PBT application needing low dyne value.

The purpose of the invention is realized by the following scheme:

the invention provides a PBT resin with a low dyne value, which comprises the following components in parts by weight:

preferably, the carboxyl end group content of the polybutylene terephthalate (PBT) resin is 18-22 mol/t, and the PBT resin with higher carboxyl end group content is preferred, so that the reactivity with PP grafted GMA is increased.

Preferably, the polypropylene GMA graft is selected from SPG-02 (Shanghai) Co., Ltd.

Preferably, the crystallization inhibitor is Cyclic Butylene Terephthalate (CBT) having the formula:

wherein n is any integer between 2 and 7. CBT-100 from Securix, USA, can be selected.

Preferably, the catalyst is anhydrous ethylene glycol antimony (CAS:29736-75-2), and ethylene glycol antimony produced by Yunnan Murray antimony industry Co.

The second aspect of the invention provides a preparation method of a low-dyne-value PBT resin, which comprises the following steps:

s1, weighing the following components in parts by weight: 100 parts of polybutylene terephthalate (PBT), 8-20 parts of polypropylene GMA graft, 0.5-2 parts of crystallization inhibitor and 0.01-0.05 part of catalyst.

S2, fully and uniformly mixing the components in the step S1 through a high-speed mixer, extruding the mixture through a double-screw extruder, and granulating to obtain the PBT resin with a low dyne value; the rotation speed of the double-screw extruder is 450-600 r/min, and the temperature is 230-240 ℃.

The PBT resin prepared by the invention has a dyne value lower than 38 and no precipitation risk, and can be applied to the fields of PCB packaging and the like which need low dyne value application.

Compared with the prior art, the invention has the following beneficial effects:

1. the low-dyne-value PBT resin has a dyne value lower than 38, has no precipitation risk, and can be applied to the fields of PCB packaging and the like which need low-dyne-value application.

2. In the PBT resin prepared by the invention, the PBT resin with high carboxyl content and the polypropylene are used for grafting GMA, and then ethylene glycol antimony is introduced into a system as a reaction catalyst, so that GMA groups and the PBT resin are fully reacted, the reaction activity between the GMA groups and the PBT resin is improved, the compatibility between the polypropylene and the PBT resin is increased, and the polypropylene resin with the characteristic of low dyne value can fully reach the surface, thereby reducing the dyne value of the composite material.

3. The PBT resin prepared by the invention is a semi-crystalline resin with coexisting crystalline state and amorphous state, because the cyclic polybutylene terephthalate (CBT) is introduced as a crystallization inhibitor, the reaction efficiency between PP grafted GMA and the PBT resin is improved, the molecular chain length of the PBT is expanded, the crystallinity of the PBT resin is reduced, the surface crystalline state content is reduced in the PBT molding cooling process, and the dyne value of the PBT resin is further reduced. Meanwhile, the CBT resin has extremely strong reaction activity, and can 'quench' residual carboxyl end groups, hydroxyl end groups, GMA and other high-polarity groups.

Detailed Description

The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that it would be obvious to those skilled in the art that various changes and modifications can be made without departing from the spirit of the invention. All falling within the scope of the present invention.

The PBT resin prepared by the invention utilizes the characteristic of low dyne value of polypropylene to reduce the dyne value of the surface of the PBT resin, but the dyne value of the PBT resin cannot be effectively reduced by simply grafting GMA with polypropylene, mainly because the compatibility of the PBT resin and PP is insufficient, the PP resin cannot be fully dispersed to the surface of a matrix, and simultaneously, a high-polarity GMA group exists, so that the GMA group needs to be fully reacted with the PBT resin.

However, the PBT resin has stable structure and low reaction activity. Therefore, when the PBT resin with high carboxyl content is used, ethylene glycol antimony is introduced into a system as a reaction catalyst, so that the reaction activity between the PBT resin and the ethylene glycol antimony is improved, the compatibility between polypropylene and the PBT resin is improved, and the polypropylene resin with the characteristic of low dyne value can fully reach the surface, thereby reducing the dyne value of the composite material.

Because the PBT resin is a semi-crystalline resin with coexisting crystalline state and amorphous state, the density of the crystalline state is higher than that of the amorphous state, and the dyne value of the crystalline state is higher than that of the amorphous state, the cyclic polybutylene terephthalate (CBT) is introduced as a crystallization inhibitor, the CBT resin has high reactivity, the crystallinity of a PBT molecular chain is reduced, the reaction efficiency between PP grafted GMA and the PBT resin is improved, the length of the PBT molecular chain is increased, the crystallinity of the PBT resin is reduced, the surface crystalline state content is reduced in the PBT molding cooling process, and the dyne value of the PBT resin is further reduced. Meanwhile, the CBT resin has extremely strong reaction activity, and can 'quench' residual carboxyl end groups, hydroxyl end groups, GMA and other high-polarity groups.

The technical solution of the present invention is described in detail below with reference to specific examples.

The PBT resin adopted in the following examples has a carboxyl end group content of 18-22 mol/t, and is purchased from PBT KH2083 produced by Yingkou Kanghui petrochemical production.

The PBT resin adopted in the comparative example has the terminal carboxyl group of 10-11mol/t and is purchased from PBT TH6100 produced by Xinjiang blue Shantun river.

The polypropylene-grafted GMA used in examples 1 to 5 and comparative examples 1 to 5 was obtained from SPG-02 manufactured by Korea Polymer (Shanghai).

The crystallization inhibitors used in examples 1-5 and comparative examples 1-5 were branched polyesters, available from CBT-100, available from Securix corporation, Wus USA.

The catalyst used in examples 1-5 and comparative examples 1-5 was ethylene glycol antimony, available from Yunnan Murray antimony industries, Inc.

The dyne values were tested as follows:

(1) selecting a dyne pen (such as specifications of 29, 30, 31, 32, 33, 34, 36, 38, 40, 42, 46, 48, 50 and the like) with a corresponding pen size according to test requirements, ensuring whether the dyne pen is in service life, wearing an electrostatic ring and a finger stall;

(2) finding a test area to ensure the surface to be clean and free from particles/dirt according to the test requirements;

(3) vertically and tightly holding the dyne pen, and vertically arranging the dyne pen on the surface of the test area; slightly pressing the pen point to draw a straight line of 5-10 cm, immediately retracting the pen, and covering a pen cap;

(4) and (3) observing whether the handwriting shrinks and is condensed into water drops or not by visual observation after 2-5 s:

a: if the water drops shrink, the dyne pen with the first-order numerical value is replaced to draw a straight line again until the water drops do not shrink and no water drop point exists, and therefore the surface dyne value of the material is determined.

B: if the handwriting is smooth and not shrunk and condensed into a water droplet point, the dyne pen with the first-level numerical value is changed to draw a straight line again until the handwriting shrinks and is condensed into the water droplet point, and the dyne pen number of the last numerical value is the surface dyne value of the material.

Example 1

The PBT resin with the low dyne value comprises the following components in parts by weight:

the preparation method of the PBT resin comprises the following steps:

(1) weighing the following components in parts by weight: polybutylene terephthalate (PBT), polypropylene GMA graft, crystallization inhibitor and catalyst.

(2) Fully and uniformly mixing the components in the step (1) through a high-speed mixer, extruding the mixture through a double-screw extruder, and granulating to obtain the PBT resin with a low dyne value; the rotation speed of the double-screw extruder is 450-600 r/min, and the temperature is 230-240 ℃.

The PBT resin thus obtained was injection-molded into a standard test specimen having a size of 10 cm. times.10 cm. times.2 cm, a trace was drawn on the specimen with a dyne pen, and the dyne value of the specimen was tested in accordance with the shrinkage of the trace.

Example 2

the preparation method is the same as example 1.

Example 3

the preparation method is the same as example 1.

Example 4

the preparation method is the same as example 1.

Example 5

the preparation method is the same as example 1.

Comparative example 1

The PBT KH2083 was injection molded into a standard test panel having dimensions of 10cm by 2cm, a dyne pen was used to draw a trace on the panel, and the dyne value of the panel was tested for the shrinkage of the trace.

Comparative example 2

Different from the embodiment 3, PBT TH6100 is selected as polybutylene terephthalate (PBT).

Comparative example 3

Unlike example 4, no polypropylene grafted GMA SPG-02 was added.

Comparative example 4

In contrast to example 2, no crystallization inhibitor CBT 100 was added.

Comparative example 5

In contrast to example 5, no catalyst ethylene glycol antimony was added.

Test results

The dyne value test results of the materials obtained in examples 1 to 5 and comparative examples 1 to 5 are shown in Table 1:

component proportions and test results for Table 1, examples 1-5 and comparative examples 1-5

From the data in Table 1, it can be found that the PBT having a low dyne value prepared by the present invention has a dyne value of 38 or less.

Comparative example 1 shows that the dyne value of the pure PBT resin is higher, and examples 1-5 show that the dyne value of the PBT is obviously reduced after the method is adopted. Comparative example 2 and example 1 show that PBT resin with high molar carboxyl content has higher reactivity with PP graft and is more effective in reducing surface dyne value. Comparative example 3 shows that in the condition of no addition of SPG-02, more polar groups remain on the surface due to the catalytic action of the ethylene glycol antimony, and the dyne value of the material is higher. Comparative example 4 shows that the main role of CBT is in crystallization inhibition and "annihilation" of the reactive groups, and that the dyne value of the material cannot be effectively reduced without the CBT group; comparative example 5 shows that ethylene glycol antimony is mainly used for catalyzing PBT to generate more reactive groups, and the reaction performance of the PBT resin with low reactivity and SPG-02 is improved.

The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes or modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention. The embodiments and features of the embodiments of the present application may be combined with each other arbitrarily without conflict.

Claims

1. The PBT resin with the low dyne value is characterized by comprising the following components in parts by weight:

2. the low-dyne-value PBT resin according to claim 1, wherein the carboxyl end group content of the polybutylene terephthalate is 18 to 22 mol/t.

3. The low-dyne PBT resin of claim 1, wherein the low-dyne PBT resin is a semi-crystalline resin.

4. The low-dyne PBT resin of claim 1, wherein said crystallization inhibitor is a branched polyester.

5. The low-dyne PBT resin of claim 4, wherein the branched polyester is cyclic butylene terephthalate.

6. The low-dyne PBT resin of claim 5, wherein the ring-shaped polybutylene terephthalate has the following structural formula:

wherein n is any integer between 2 and 7.

7. The low dyne PBT resin of claim 1, wherein the catalyst is anhydrous ethylene glycol antimony.

8. A process for preparing the low-dyne PBT resin of claim 1, comprising the steps of:

s1, weighing the following components in parts by weight: 100 parts of polybutylene terephthalate, 8-20 parts of polypropylene GMA graft, 0.5-2 parts of crystallization inhibitor and 0.01-0.05 part of catalyst;

s2, mixing the components in the step S1 uniformly, extruding and granulating to obtain the PBT resin with low dyne value.

9. The method for preparing the PBT resin with the low dyne value as claimed in claim 8, wherein the rotation speed of the twin-screw extruder used for the extrusion granulation is 450-600 rpm, and the temperature is 230-240 ℃.